Amidoximes and amidhydrazones and method of preparation



United States Patent E 2 Int. Cl. C07c 123/00, 129/00, 133/00 US. or. 260-564 10 Claims ABSTRACT OF THE DISCLOSURE Amidoximes and amidhydrazones are produced by reacting aminoacetylene compounds with hydroxylamine and hydrazine, respectively. The amidoximes and amidhydrazones are hydrolyzed to give amides and hydroxylamine or hydrazine.

This application is a continuation-in-part of application Ser. No. 414,852, filed Nov. 30, 1964, and now US. Patent No. 3,437,663 which is in turn a continuation-inpart of application Ser. No. 376,253, filed June 18, 1964, and now US. Patent No. 3,340,246.

This invention relates to addition reactions. More particularly, the invention is directed to chemical reactions in which a chemical compound containing an active hydrogen atom adds to the triple bond of an aminoacetylene.

As used herein, the term active hydrogen means a hydrogen atom which is more easily dissociated from the atom to which it is bonded than is a hydrogen atom bonded to carbon in a hydrocarbon molecule. The term addition reaction as used herein, means the chemical reaction which takes place with the breaking of the bond between an active hydrogen atom and the moiety to which it is initially attached and the formation of new bonds (a) between the hydrogen atom and one carbon of the aminoacetylene triple bond, and (b) between the moiety originally carrying the active hydrogen atom and the other carbon atom of the aminoacetylene triple bond. Following this initial addition reaction, the aminoacetylene derivative may or may not undergo further rearrangement.

It has now been discovered that aminoacetylenes undergo a variety of addition reactions with compounds containing active hydrogen atoms with the production of a wide variety of novel chemical compounds. It is therefore an object of this invention to provide a process for adding compounds containing active hydrogen atoms to aminoacetylenes. A further object of the invention is to provide a process in which aminoacetylenes react with compounds containing active hydrogen atoms including alcohols, amines, hydrogen halides, hydroxyl amine and hydrazine. A still further object of the invention is to provide novel chemical compounds which are derivatives of aminoacctylenes.

According to the process of this invention, an aminoacetylene compound and a compound containing at least one active hydrogen atom are mixed together and maintained at a temperature sufiiciently elevated to cause'addition of the active hydrogen compound to the triple bond in the aminoacetylene.

The aminoacetylene compounds useful in the process of this invention are those represented by the formula YCECN wherein R is a monovalent hydrocarbon group, Y is an R group, a hydrogen atom or an NR group, and two R ice groups on the same nitrogen atom can together form a divalent alkylene group or a divalent alkylene ether group.

In the compounds of Formula A the various R groups can be the same or different throughout the same molecule, and the R groups preferably contain from 1 to about 18 carbon atoms.

The R groups in Formula A can be alkyl, aryl, alkaryl, aralkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and the like groups. For example, R can be methyl, ethyl, n-butyl, tertiary butyl, 2,2 dimethyl n propyl, iso octyl, octadecyl, phenyl, phenylethyl, terphenyl, cumyl, mesityl, cyclopentyl, ethylcyclohexenyl, allyl, or butyne 2 yl groups, and the like, and two R groups on the same nitrogen atom can together be tetramethylene, 3-ethylhexamethylene, decamethylene, and the like.

Throughout the present specification and claims, C H Cal I11 C6H5, C6H4, C H i-C4H and t-C4H represent respectively the ethyl, cyclohexyl, phenyl, phenylene, normal butyl, isobutyl and tertiary butyl groups.

Typical compounds represented by Formula A are the following:

NCECQ CH t-CaHoECN The compounds of Formula A can be prepared by the re- (iii) (v ii) In Formulas ii, iii, iv, v, vi and vii, R has the meaning defined hereinabove with reference to Formula A, R represents hydrogen or an R group, X represents a halogen, preferably fluorine, chlorine, or bromine, and M represents an alkali metal, namely, lithium, potassium, rubidium, cesium or francium.

The process for producing the compounds of Formula A comprise mixing together in a hydrocarbon, hydrocarbon ether or tertiary amine solvent a compound of Formula ii, iii, iv or v and a compound of Formula vi or vii, and maintaining the mixture at a temperature between about 25 C. and 150 C. until the compound of Formula A is produced. Preferably, the reactants are employed in the ratio of at least one mole of the compound of Formula vi or vii per gram atom of halogen in the compound of Formula ii, iii, iv, or v. A slight excess of the compound of Formula vi or vii over and above this ratio is often desirable. Preferably the reaction mixture is stirred during the course of the reaction.

It is preferable to carry out the reaction producing compounds of Formula A under anhydrous conditions and in the absence of oxygen. This can be conveniently done by carrying out the reaction under an atmosphere of inert gas, such as nitrogen, argon, helium, and the like.

Organic solvents useful in this process include hydrocarbons, hydrocarbon ethers, and tertiary amines represented by Formula vii hereinabove. Illustrative solvents include hydrocarbons such as petroleum ether, cyclohexane, 2-ethylhexane, benzene, toluene, xylene and the like,

, and ethers such as diethyl ether, di-isopropyl ether,

methylbutyi ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and the like, and tertiary amines of Formula vii hereinabove. v

Where highly volatile reactants, such as HCECF, t-C H CHBrCHBrF or CHF CCI are employed, it is preferable to form the reaction mixture at -80 C' or below and then warm the mixture to -20 C. to 25 C. where reaction will take place.

Compounds of the formula R NCECNR (Y in Formula A is NR can be produced by the reaction of a compound of the formula HXC=CFX with a compound of Formula vi. The reaction mixture is preferably formed at -80 C. or below and the reaction takes place on warming to room temperature. Where a mixture of compounds of Formula vi is employed, compounds of the formula R NCECNR are produced wherein the two R N groups are different, I

Where R in Formula ii is hydrogen, the reaction of a compound of Formula ii with a compound of Formula vi first produces a compound having the formula MCECNR which on treatment with an aliphatic alcohol gives the desired compound HCECNRZ.

LiN( CH CH 2 and N(CH gives a mixture of C5H5CECN(cH and C H CECN(CH CH The relative amounts of products in such product mixtures depend on the relative reactivities of the compounds of Formulas vi and vii. In such reactant mixtures, the compound of Formula vii is both a reactant and a solvent.

Where a compound of Formula vii is used, and the R groups are not all the same, the primary product will depend on which nitrogen-R group bond is most easily broken. It has been found, for example, that a typical order of decreasing ease of RN bond breaking is allyl- N, benzyl-N, methyl-N, ethyl-N, and n-propyl-N. Thus, the reaction of C5H5CEccl with cHFN-omonn C H2CH2 yields primarily CaHsCECN CHZCHs When the solvent is a hydrocarbon or hydrocarbon ether, the preferred reaction temperatures are 25 C. to 20 C., and when the solvent is a tertiary amine, higher temperatures up to 150 C. are preferred.

There is no particular advantage to be gained in carrying out the reaction at pressures other than atmospheric pressure. However, when a sealed reaction vessel is employed, the autogeneous pressure of the reaction mixture at the reaction temperature is satisfactory.

Formation of the compound of Formula A in good yield generally takes from a few hours up to several days depending on the particular temperature, solvent and reactants.

The reaction product, a compound'of Formula A, is separated from the reaction mixture by conventional methods which include separation of liquid from precipitated salts and other solids, and isolation of the desired product by evaporation of solvent, fractional distillation, and the like. Product separation is preferably carried out under an inert atmosphere.

Examples of producing compounds of Formula A (underlined) are the following:

(a) -20C.to 25C.

diethyl ether CuH5CECN(CHa)2 LiOl CaHsCEC C1 LiN(CHs)2 diethyl ether HGEON(OH3)2 (omnonom 80 C. to 20C diethyl ether 80 C. to C diethyl ether (g 80 C to 20 C ROH (C) GNH and wherein R has the meaning defined hereinabove with reference to Formula A; G is an R group, a hydroxyl group OH, or a primary amine group NH and X is a halogen, namely, fluorine, chlorine, bromine, iodine or astatine.

Typical compounds represented by Formula B are methanol, ethanol, t-butanol, 2-ethyl-6-hexanol, octadecanol, phenol, m-cresol, benzyl alcohol, allyl alcohol, cyclohexanol, propargyl alcohol, beta-phenylethanol, and the like.

Typical compounds represented by Formula C are methyl amine, ethyl amine, t-butyl amine, Z-aminoheptane, octadecyl amine, aniline, p-ethylaniline, beta-phenylethyl amine, allyl amine, 1-amino-3-butyne, cylcoheptyl amine, and the like.

The compounds of Formulas B and C, and the hydrogen halides of Formula D are well known and can be prepared by conventional methods.

The process of this invention can be used to produce a wide variety of new and useful chemical compounds, for example, the reaction of a compound of Formula A with a compound of Formula B (ROH) produces compounds having the formula Typical compounds represented by Formula E are the following:

HOH:

The reaction of compounds of Formula A with compounds of the formula RNH produces compounds represented by the formula YCHz-CN R NR wherein Y and R have the meanings defined hereinabove.

, Illustrative compounds represented by Formula F are the following CH3 HaCCfi CH2CH2CH3 NCH2(CH3)5CH3 CHzCaHs CHaCaHqCHzCN N CH3 CH CHCH2CH2CH CHzCH2CH=CH2 t-C4H9OH2-CN t CHzCrHrCHa NCqHlCHZCHa CHzCHz CH2 CH2C NCH2CH=CH2 CHzCHa CHaCHzOHz NCH2CN CHaCH2CH3 CH CHaCHzCHz-CH2-CN H CHzCHg Compounds of Formula E and Formula F react with hydrogen halides and are therefore useful under anhydrous conditions as hydrogen halide acceptors. For example, all of the compounds of Formulas E and F can be used as hydrogen halide acceptors in the process for producing cyclopentadienyl metal compounds described in Morehouse, US. Patent 3,071,605, issued Jan. 1, 1963.

The reaction of compounds of Formula A with hydroxylamine produces compounds represented by the formula YoHr-ofi NOE wherein Y and R have the meanings defined hereinabove. Illustrative compounds of Formula Gare the following NOH CHzCtHaCHa CHaCaHlCHr-CN CHaCHzCHa NOH CHzCHa CH2 CHzCa NOH NCHzCN r CHgGH? sHa NOE Compounds of Formula G are useful as sources of hydroxyl amine for use in chemical reactions. Compounds of Formula G hydrolyze readily to release hydroxylamine and amides of the formula The reaction of compounds of Formula A with hydrazine produces compounds represented by the formula wherein Y and R have the meanings defined hereinabove. Illustrative compounds of Formula H are the following CH II3=NN=(J CH 011305114 CH3 CH3 C CH2 CH:

CHaCHzCaHq NCHzC CH3CH2C6H4 N CHsCHz CGHCHZC S CHzCHa C Hz C H3 The reaction of compounds of Formula A with hydrogen halides (compounds of Formula D) produces compounds represented by the formula .8 wherein Y, R and X have the meanings defined hereinabove. Illustrative compounds of Formula I" are the following HaCCN on,- Dr 011206115 c'ancnanornon I CH3 Br can 01 can,

t-olntonzosr can 1' onions NCHaCN I CH2 CeHs 1 orno Compounds of Formula I are "useful as halogenation reagents in the productionof hydrocarbon halides from alcohols and the production of acid halides from acids. For example, a compound of Formula I reacts with an alcohol ROH to produce the hydrocarbon halide RX plus the by-products HX and amides of the formula YGHzONRz The process of the present invention can be carried out with or without a solvent. However, an inert organic solvent is preferred. Suitable inert solvents include hydrocarbons, halogenated hydrocarbons, and hydrocarbon ethers, for example, hydrocarbons such as petroleum ether, cyclohexane, 2-ethylhexane, benzene, toluene, xylene .and the like, and ethers such as diethyl ether, diisopropyl ether, methylbutyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and the like, and inert halogenated hydrocarbons such as methylene chloride, trichloroethane, chlorobenzene, bromobenzene, and the like.

' The temperatures at which the process of this invention is carriedout can vary widely depending upon the particular reactants, and .the proper choice of temperature is, illustrated by the examples hereinbelow. Usually temperatures from about .20 C. up to about 100 C., and preferably from room temperature up to about 50 C., are satisfactory, except in the case of reactions with hydrogen halides where initial temperatures of C. or below are preferred. When a solvent is employed, the boiling point of the solvent isoften a convenient elevated temperature; I

. There is no particular advantage to be gained in carrying out the process of this invention at pressureother than atmospheric pressure. However, when a sealed reaction vessel is employed, the autogeneous pressure of the reaction mixture at the reaction temperature is satisfactory.

Although not absolutely necessary, it is preferable to employ trace amounts of mineral acid as a catalyst for the addition reaction of the process of this invention. Suitable catalysts include hydrochloric acid, hydrobromic acid, sulfuric acid, and the like..Whenthe active hydrogen compound employed in the process of this invention is allydrogenhalide, no separate additional catalyst is required.

Since aminoacetylenes react readily with water, it is preferable to carry out the process of this invention under anhydrous conditions. This may be conveniently done by carrying out the process of this invention under an atmosphere of inert gas such as nitrogen, helium, argon, and the like.

The addition reaction of the process of this invention takes place in good yield in reaction times of from a few minutes up to several days depending on the particular temperature, solvent, presence or absence of catalyst, the particular reactants, and the like.

The products produced by the process of this invention can be separated from the reaction mixture by conventional methods including separation of liquid products from solid matter, the isolation of the desired product by evaporation of solvent, fractional distillation, and the like. Several methods of product recovery are illustrated in the examples hereinbelow.

The ratio of reactants in the process of this invention is not critical. However, it is frequently preferable to employ the active hydrogen-containing compound in amounts which correspond to either one or two gram atoms of active hydrogen per gram mole of aminoacetylene. For example, in preparation of compounds of Formula E, it is preferable to employ one gram mole of ROH per gram mole of aminoacetylene, while in production of compounds of Formula I, it is preferable to employ two gram moles of hydrogen halide per gram mole of aminoacetylene.

In some instances the compounds produced by the process of this invention undergo a rearrangement following the initial addition reaction. For example, the compounds of Formula I rearrange to form an equilibrium mixture of the equilibrium favoring the salt form.

Also compounds produced by the addition of two moles of ROH to a compound of Formula A rearrange to form an equilibrium mixture of the equilibrium concentration of the salt-like form being extremely small.

The active hydrogen containing compounds useful in the process of this invention can contain more than one site which is reactive in the process of this invention. For example, hydrazine contains two H2N- groups, both of which are reactive sites in the process of this invention. Other examples are glycols, triols, diamines, dithiols, and the like.

Other classes of active hydrogen compounds which are useful in the process of this invention include hydrogen cyanide, ammonia, hydrogen sulfide and compounds having the formulas (J) RSH (L) HOROH HSR"SH and (O) R NH wherein R has the meaning defined hereinabove and R" is a divalent hydrocarbon group such as ethylene, 1,2- propylene, 1,4-butylene, 1,4-cyclohexylene, para-phenylene and the like.

Other reactions which further illustrate the process of this invention are the following:

In some instances the compounds produced by the process of this invention react with a strong base to regenerate the compound of Formula A. For example, the compounds of Formula I (equilibrium mixture) react with compounds of Formula vi according to the equation (k) HCECN(C&H5)2 CaHsPHz The reaction is conveniently carried out by mixing the compounds of Formulas I and vi, preferably in an inert hydrocarbon or hydrocarbon ether solvent of the classes described hereinabove, at a temperature of about 0 C., or below (temperatures as low as C. have been used), and then maintaining the reaction mixture at a temperature between about 25 C. or lower and about 50 C. or higher until the compound of Formula A is produced. A good yield of the compound of Formula A is generally obtained in about one hour. This reaction is further illustrated in the examples hereinbelow.

As another example, the compounds produced by the reaction of compounds of Formula A with compounds of Formula I and having the formula (P) YOH=CNR2 wherein Y and R have the meanings defined hereinabove, react with strong bases such as the compounds of Formula vi or sodamide' (NaNH to regenerate the compound of Formula A. When a compound of Formula vi is used as the strong base, it is preferable to use a hydrocarbon ether solvent and a temperature of about room temperature up to the boiling point of the solvent. When NaNH is used, compounds of Formula vii and very strongly basic organic amines such as piperidine are convenient solvents and temperatures from room temperature to the boiling point of the solvent are employed. Solid NaNH can be used by passing vapors of the compound of Formula P at reduced pressure (about 1 mm. Hg) over the solid base at temperatures in the range of about C. to 200 C.

The following examples further illustrate the process and compounds of this invention.

EXAMPLE 1 A mixture containing 0.005 mol of 1-phenyl-2-dimethylaminoacetylene and ethanol in 5 ml. diethyl ether was kept overnight at room temperature. A trace of anhydrous HCl was used as a catalyst. The solvent was then evaporated and the residue distilled at C./0.005 mm./Hg to yield beta-dimethylamino-beta-ethoxystyrene. A field ionization mass spectroscopic determination of molecular weight yielded the theoretical value. To further prove the structure, the product beta-dimethylamino-beta-ethoxystyrene was hydrolyzed at room temperature with 6 normal HCl to yield ethyl-alpha-phenyl-acetate and the 00- product dimethylamine.

EXAMPLE 2 Into a solution of 0.59 g. of 1-phenyl-2-dimethylaminoacetylene in 50 ml. of n-hexane was introduced a stream of dry HCl at -80 C. A white solid precipitated. The product (2-phenyl-1,1-dichloroethyl) dimethylamine was analyzed for chlorine:

Calculated for C H Cl N (percent): CI, 32.5. Found (percent): Cl, 31.7.

1 1 EXAMPLE 3 N,N,N',N-tetraethyldiaminoacetylene (0.941 g.-=0.005 mole) and aniline (0.416 g.=0.005 mole) were dissolved in ml. diethyl ether. When 0.8 ml. of a 0.665 normal solution of HCl in diethyl ether was added a small amount of aniline hydrochloride precipitated. The solvent was evaporated from the ethereal solution and the residue distilled under 0.002 mm./Hg. At 115 C. 1.1 g. of the N phenylamidine of N,N diethylalpha(diethylamino)- acetamide was obtained which is redistilled at 110 C./0.002 mm. Hg. Yield: 80%.

Analysis.Calcd. for c15H27N (percent): C, 73.51; H, 10.41; N, 16.08; M.W.=261.40. Found (percent): C, 72.61; H, 10.25; N, 15.40; M.W.; 261 (Determined by EXAMPLE 7 osmometry): Calcd for C H N (percent): C, 74.50; H, 8.13; N,

V 17.38; M.W., 322.4. Found (percent): C, 74.55; H, 8.06;

field ionization mass spectrometry). N, 17.45; M.W., 330. I

EXAMPLE 4 EXAMPLE 8 Following the general procedures of Example 3, th A solution of ,1 t-butyl- 2 dimethylaminoacetylene process of this invention was used to produce the follow- (0.005 mole) in 10 ml. of acetonitrile was added to a soing N-trisubstituted amidines: 29 lution of 2,4-dinitrophenylhydrazone (0.0055 mole) in 50 Aminoacetylene Primary amine Boiling or Melting Point I reactant reactant Amidine product C.)

OBH5CECN(CH3)2. CuHaNHz CuHaCHzCNflDHQz M.P.9899

NCBH5 t-O4HBC CN(CH3) 2.-.. CuH5NH2 t-C;H9OHzh3N(CH )2 BI. 120/0002 mm. Hg

NCcHs t-C4H C=CN(CHa)2 Alphanaphthylarnine t-C1H CHzON(CHa)2 B.P. 115120, 0.002 mm. Hg

N(alphanaphthyl) EXAMPLE 5 ml. of acetonitrile at room temperature The resulting red lution was concentrated by evaporating part of the sol- Hydroxylamme was prepared by CllSSOlVlll" (with so stirring) 0.8 gram, 0.015 mole) of finely ground hydroxgigz gg ggzf at room temperature The amldhy' ylamine hydrochloride in a mixture of ml. chloroform P and 5 ml. triethylamine. Diethyl ether was then added to tmmcHzoNwHm precipitate diethylamine hydrochloride which was sepal rated, leaving hydroxylamine in solution. Next, 1.45 40 grams (0.01 mole) of 1-phenyl-2-dimethylaminoacetylene were added to the hydroxylarnine solution. The solvents N02 were immediately evaporated under vacuum at room temcrystallized from the concentrated solution at room temperature and the residue was recrystallized from ethanol perature. The product, recrystallized from acetonitrile, had to give the amidoxime a melting point of 190 C. and gave the following analysis 49 (molecular weight by osrnometry): eHCH2CN(CHs)2 Calcd for C H O N (percent): C, 52.02; H,6.36; N011 N, 21.66; M.W., 323.35. Found (percent): C, 52.05; H, 1 146 147 C 6.58;N, 21.40; M.W., 317. me ting point Analysis.Calcd, for C H ON (percent): C, 67.39; 50 EXAMPLE 9 H, 7.91; N, 15.71. Found (percent): C, 67.35; H, 7.90; Lithium diethylarnide was added to a suspension of the N, 15.60. (2-phenyl-1,1-dichloroethyl) dimethylamine [the product EXAMPLE of Example 2] in diethyl ether at 80 C. The solid material dissolved on warming the mlxture to room tempera- Followmg the general procedures of Examp e .5, lture. The solvent was evaporated and 1-pheny1-2-dimethylbutyl 2 dimethylar n1noacetylene and hydroxylamine reacetylene was recovered from the residue. acted to give the amidoxlme EXAMPLE 10 "(MHYCHNMOHW In several additional examples, compounds of Formula NOH I (equilibrium mixture) were mixed with compounds of o Formula vi in hydrocarbon ether solvents at about 0 C. m g P 114 (from Petroleum ether), 111 73% and then maintained at room temperature for'about an y hour. The solvent was evaporated and the compound of y C'IHIBONZ (P Formula A recovered from the residue byfractional dis- H, 11.47; N, 17.71. Found (percent): 0, 60.72; H, 16.41;

tillation. The results are summarized in the following table: i

Formula (vi) B Formula I Reactant Reactant Product Pzrhz h t CH3CHz=(|}N(GgH Cl- LKCzHs): (EH30 E CN(C2H.',)2 60-62/90 mm. Hg 39 CHsCHz=(|3N(C:H )2, C1 CHaC E ON(C2H5)2 60-62/90 mm. Hg 58 Formula (vi) Boiling Point, Yield, Formula. I Reactant Reactant Product C. Percent CHgCHz CHaGHz CHaOHFCN CH2, C1- LiN(CHs)2 CHaC E CN CH2 72-73/15 mm. Hg 12 Cl CH2CH2 CHzOfiz CHzCHz CHzCHg CH3CH2=CN CH2, Cl- LiN(C2Hs)2 CHaC ON CH1 72-73/15 mm. Hg 39 c1 CHzCHz omen,

CHzCHz CHzCHZ CH3CHFCN CH1, Cl- LlN(CHzCH2CHa)2 CHzC CN CH: 72-73/15 mm. Hg Trace ll CHzCH: CHzCHz CHzCHz v CHzCH-g CH OHz=C IS CH2, c1- LiN(CaHu)2 CHSC CN CH 72-73/15 mm. Hg 46 (I31 CHzCHa CH2CH2 C2H5CH2=C(CzH5)2, C1 LiN(CzH5)2 C2H5CECN C2H5)2 50-51/30 mm. Hg 38 C2H5CH C(C2HB)2, C1 LiN(Cs u)2 2 5 CN(C2 5)2 50-51/30 mm. Hg 77 G4 aCHF (C2 s)2, C1 LiN(C2 s)2 C4H9CECN(C2H5)2 77-78/15 mm. Hg 29 CHFC(C2H5)z, Cl- L N( 2 s): H N( zHs)2 About 10 EXAMPLE 11 What is claimed is: Following the methods described hereinabove, com- Compounds represented by the formula pounds of Formula P were caused to react with strong R bases to give compounds of Formula A. The results are YCHPCN summarized in the table hereinbelow. 40 IHIOH R The products set forth in the table, and the class of aminoacetylene compounds having the formula Q) CHaCHz CHzCH:

wherein R has the meaning defined hereinabove, can be produced by the reaction of a compound of Formula it with is useful as hydrogen halide acceptors in the same manner as compounds of Formulas E and F.

wherein R is a monovalent hydrocarbon group containing from one to about 18 carbon atoms, Y is selected from the class consisting of R groups, hydrogen and NR groups, and two R groups on the same nitrogen atom can together form an alkylene group.

2. Compounds represented by the formula NR groups, and two R groups on the same nitrogen atom can together form an alkylene group.-

Yield Formula P reactant Strong base Reactor conditions Product erc t /CH C2 CHzCHg CaH5CH= CN 0 Li(C2H5)2 Tetrahydrofuran solvent, room temp., NZ atmos- CaH5C 2 ON 0 40 phere, 2-3 hours. CHrCHz CHzCHg S 011 B.P. 99-100" C./0.0l mm. Hg. Same as above Solid NS-NHz-.- Vapor phase, 1 mm. Hg. 165 C Same as above 50 Do NaNHz Pgpfizidine solvent, refluxtemp, N2 atmosphere, ..do 50 ours.

CHzCHz CHQCH: H2C=C /0 NBNH: do HC CN 0 About 5 CH2CH2 HzOH:

S CH3 15 3. The amidoxime'represented by the formula eiHsoHzcmc Hm I NOH V 4. The amidoxime represented by the formula t-C4HaCHzCN(CH )2 NOH 5. The amidhydrazone represented by the formula CQH5CH2G=NN=CCHC5H5 s)2 N( a)2 6. The a'midhydrazone represented by the formula t-C4H9CH2ON(CH3)2 7. The process which comprises 1) mixing together (a) an aminoacetylene of the formula YCECNR wherein R represents a monovalent hydrocarbon group of from 1 to 18 carbon atoms, two R groups on the same nitrogen atom can together form an alkylene group, or two R groups on the same nitrogen atom can when taken together with the nitrogen atom to which they are attached form a morpholino group, and wherein Y represents an R group, a hydrogen atom, or an -NR group, and (b) a compound of the formula RNH wherein R has the meaning discussed above, hydrazine, or hydroxylamine, and (2) maintaining said mixture at a temperature within the range of from about '-20 C. to +100 C. for a period of time sufiicient to cause the addition of said compound to the triple bond of said aminoacetylene.

' ...hydroxylarnine,. .and. wherein the "16 V 9.--Th e' process of claim 7 wherein said compound is product of the process is a compound of the formula:

NOH R wherein Y and R are as defined in claim 7.

10. The process of claim -7 wherein said compound is hydrazine, and wherein the product of the process is a compou'nd of the formula:

References Cited FOREIGN PATENTS 8/1959 Belgium.

OTHER REFERENCES Baksheev et al., C.A., vol. 47, pp. 8641-8642 (1953). Braun et 211., CA. vol. 23, pp. 3207 to 3208 (1929). Hunter et al., C.A., vol. 36, pp. 1320 to 1321 (1942). Kruse et al., I. Am. Chem. Soc., vol. 83, pp. 213 to 8. The process of claim 7 wherein said compound is wherein Y and R are as defined in claim 7.

H Oxley et al., C.A., vol. 43, pp. 2593 to 2595 (1949).

Seefelder, C.A., vol. 55, p. 165706 (1961). Shigorin et a1. C.A., vol. 40, pp. 831,3,4, (1946).

D HIGEL, Primary Examiner US. :1. X.R. 

